Binder resin and synergist composition including a parting agent and process of making lignocellulosic

ABSTRACT

A method for preparing compression molded or pressed lignocellulosic articles is disclosed. The method involves forming a binder resin by combining a polyisocyanate component with a parting agent and preferably a synergist. The parting agent is the reaction product of an isocyanate compound and an isocyanate-reactive compound of the general structure R—(ao) n —Y where: R is a hydrophobic group containing alkyl, alkaryl, polyaryl, or siloxane moieties; (ao) is an alkylene oxide or mixture of alkylene oxides; n is from 1 to 25; and Y represents a monofunctional isocyanate-reactive group. A resinated lignocellulosic mixture is formed by combining the binder resin with lignocellulosic particles. Then a compression molded or pressed lignocellulosic article is formed by compressing the resinated lignocellulosic mixture at an elevated temperature and under pressure. It is particularly preferred that the binder resin further include a synergist of either a C 1-4  N-alkylpyrrolidone, gamma-butyrolactone, or a mixtures of them. The most preferred synergist is N-methyl-2-pyrrolidine.

FIELD OF THE INVENTION

The invention relates to a process for making compression molded orpressed lignocellulosic articles by adding a binder resin including aparting agent to lignocellulosic particles and thereafter eitherpressing the mixture between plates or compressing it in a mold at anelevated temperature and pressure and, more specifically, a method formaking compression molded or pressed boards using a binder resincomprising a polyisocyanate component, a parting agent and a synergistcomponent.

BACKGROUND OF THE INVENTION

It is known to make compression molded or pressed lignocellulosicarticles, such as particle board, Medium Density Fiberboard (MDF)agrifiber board (such as straw board or bagasse, etc.), and orientedstrand board, by coating or contacting lignocellulosic particles with abinder resin to form a lignocellulosic mixture, optionally adding otheradditives including parting agents or wood preservatives and compressingthe mixture at elevated temperatures and pressures for a time sufficientto make commercially useful articles, such as, boards.

The lignocellulosic particles can be in the form of chips, shavings,strands, wafers, fibers, sawdust, bagasse, straw and wood wool. When theparticles are relatively larger in size, the boards produced by theprocess are known in the art under the general term of engineered wood.These engineered woods include panels, laminated strand lumber, orientedstrand board, parallel strand lumber, and laminated veneer lumber. Whenthe lignocellulosic particles are relatively smaller, the boards areknown in the art as particleboard and fiber board.

The engineered wood products were developed because of the increasingscarcity of suitably sized tree trunks for cutting lumber. Such productscan have advantageous physical properties such as strength andstability. Another advantage of the engineered wood and particle boardsis that they can be made from the waste material generated by processingother wood and lignocellulosic materials. This leads to efficiencies andenergy savings from the recycling process, and saves landfill space.

The binder used to make the lignocellulosic articles is typically aresinous material. One common class of binders are resins produced bypolymerizing formaldehyde with other resin forming monomers, includingurea, melamine, and phenol. In certain applications, articles made withsuch binders are deficient in some property such as water resistance.

Another class of binders are the organic diisocyanate or polyisocyanatebinders. One of the advantages of this class is its superior resistanceto water. A disadvantage of the typical isocyanate binders is theirrelatively high viscosity, which can lead to problems with delivery ofthe binder onto the particles. This high viscosity also requires thatexcess binder be used to fully coat the particles.

In the past various solvents have been added to the polyisocyanatebinder compositions with the aim of achieving a lower viscosity andbetter handling properties. After application, the solvent generallyevaporates during the molding process, leaving the bound particlesbehind. One major disadvantage of prior art solvents is that they causea reduction in the physical properties of the formed board including areduction in the internal bond strength of the formed board.

For example, it is known to use dialkyl carbonate solvents in isocyanatebinder compositions for coating lignocellulosic particles prior tocompression at high temperature and pressure to make manufacturedlignocellulosic articles. The isocyanate binder compositions withdialkyl carbonates are reported to have a lower viscosity than the freeisocyanates, leading to advantages in their use in the process.

In the above examples, however, the use of the solvent system does notlower the amount of isocyanate binder composition required for achievingbest results, also the solvent systems generally lower the physicalproperties of the produced board.

It is therefore an object of the present invention to provide a solventsystem for an isocyanate binder composition, which will not only act asa diluent but also increase the efficiency of the binder resin when itis used to coat or contact lignocellulosic particles prior to pressingat high temperature and pressure.

Another common disadvantage of the use of isocyanate binder resins istheir poor release properties from molds or press parts used to formlignocellulosic articles, which can lead to problems during manufactureof the lignocellulosic articles when the mold or press parts stick tothe articles.

To overcome the sticking, it is desirable to use a parting agent eitherinternally as a component of the binder resin, or externally by applyingit to the press parts between runs. External parting or release agentsare less preferred because their use involves the extra step of applyingthe agents to the press parts.

It is therefore, an object of the present invention to provide a partingagent for an isocyanate binder resin, which will not only display thedesired parting properties but will also be compatible with anisocyanate binder resin.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is a method for preparing acompression molded or pressed lignocellulosic article comprising thesteps of: forming a binder resin by combining from about 75 to 99.5weight percent based on the total weight of the binder resin of apolyisocyanate component with from about 25 to 0.5 weight percent basedon the total weight of the binder resin of a parting agent, comprisingthe reaction product of an isocyanate compound and anisocyanate-reactive compound of the general structure

R—(ao)_(n)Y

wherein R is a hydrophobic group containing alkyl, alkaryl, polyaryl, orsiloxane moieties, wherein the alkyl moieties comprise straight chain orbranched hydrocarbons with 6 or more carbon atoms, the alkaryl moietiescomprise monoalkyl, dialkyl, or trialkyl substituted aromatichydrocarbons with 9 or more carbon atoms, the polyaryl moieties comprisea polyphenyl structure that is either alkyl substituted orunsubstituted, and the siloxane moieties comprise a trisiloxane orhigher polysiloxane; (ao) is an alkylene oxide or mixture of alkyleneoxides selected from the group consisting of ethylene oxide, propyleneoxide, butylene oxide, and mixtures thereof; n is from 1 to 25; and Yrepresents a monofunctional isocyanate-reactive group. In a second stepa resinated lignocellulosic mixture is formed by combining from about 1to 10 weight percent based on the total weight of the lignocellulosicmixture of the binder resin with from about 99 to 90 weight percentbased on the total weight of the lignocellulosic mixture oflignocellulosic particles, the lignocellulosic particles having amoisture content of from 2 to 15 weight percent. Then a compressionmolded or pressed lignocellulosic article is formed by compressing theresinated lignocellulosic mixture at an elevated temperature and underpressure. It is particularly preferred that the binder resin furtherinclude a synergist selected from the group consisting of C₁₋₄N-alkylpyrrolidones, gamma-butyrolactone, and mixtures thereof. The mostpreferred synergist is N-methyl-2-pyrrolidine.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION

In accordance with the present invention there is disclosed a processthat utilizes an isocyanate binder resin for the preparation oflignocellulosic articles. The binder resin comprises an organic di- orpolyisocyanate, a parting agent and optionally, a synergist selectedfrom the group consisting of C₁-C₄ N-alkyl pyrrolidones,gamma-butyrolactone, and mixtures thereof. Throughout the presentspecification and claims the terms compression molded or pressed areintended to refer to the same process whereby the article is formed byeither compression molding the article in a mold or by using compressionas between a pair of plates from a press. In both procedures pressureand heat are used to form the article and to set the binder.

In the present specification and claims the term polyisocyanatecomponent is intended to include a single polyisocyanate and mixtures ofpolyisocyanates. The isocyanate compounds useful in the presentinvention comprise the organic di- and polyisocyanates, modifiedisocyanates, isocyanate-terminated prepolymers, and mixtures of theseisocyanates, all described below. Organic polyisocyanates which may beused include aliphatic, alicyclic and aromatic polyisocyanatescharacterized by containing two or more isocyanate groups. Suchpolyisocyanates include the diisocyanates and higher functionalityisocyanates, particularly the aromatic polyisocyanates. Mixtures ofpolyisocyanates which may be used include, crude mixtures of di- andhigher functionality polyisocyanates produced by phosgenation ofaniline-formaldehyde condensates or as prepared by the thermaldecomposition of the corresponding carbamates dissolved in a suitablesolvent, as described in U.S. Pat. No. 3,962,302 and U.S. Pat. No.3,919,279, the disclosures of which are incorporated herein byreference, both known as crude diphenylmethane diisocyanate (MDI) orpolymeric MDI. The organic polyisocyanate may be isocyanate-terminatedprepolymers made by reacting under standard known conditions, an excessof a polyisocyanate with a polyol which, on a polyisocyanate to polyolbasis, may range from about 20:1 to 2:1. The polyols include, forexample, polyethylene glycol, polypropylene glycol, diethylene glycolmonobutyl ether, ethylene glycol monoethyl ether, triethylene glycol,etc., as well as glycols or polyglycols partially esterified withcarboxylic acids including polyester polyols and polyether polyols.

The organic polyisocyanates or isocyanate-terminated prepolymer may alsobe used in the form of an aqueous emulsion by mixing such materials withwater in the presence of an emulsifying agent. The isocyanate compoundmay also be modified isocyanates, such as, carbodiimides, allophanates,isocyanurates, and biurets.

Also illustrative of the di- or polyisocyanates which may be employedare, for example: toluene-2,4- and 2,6-diisocyanates or mixturesthereof; diphenylmethane-4,4′-diisocyanate anddiphenylmethane-2,4′-diisocyanate or mixtures of same, the mixturespreferably containing about 10 parts by weight 2,4′- or higher, makingthem liquid at room temperature; polymethylene polyphenyl isocyanates;naphthalene-1,5-diisocyanate; 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; triphenyl-methane triisocyanate;hexamethylene diisocyanate; 3,3′-ditolylene-4,4-diisocyanate; butylene1,4-diisocyanate; octylene-1,8-diisocyanate; 4-chloro-1,3-phenylenediisocyanate; 1,4-, 1,3-, and 1,2-cyclohexylene diisocyanates; and, ingeneral, the polyisocyanates disclosed in U.S. Pat. No. 3,577,358, thedisclosure of which is incorporated herein by reference. Preferredpolyisocyanates include 2,4′-MDI, 4,4′-MDI, 2,2′-MDI, polymeric MDI, andmixtures thereof.

Typical of the preferred isocyanates are those sold under the trademarkLupranate® by BASF Corporation. For example Lupranate® , an isomericblend of 2,4′ and 4,4′ MDI isomers or Lupranate® M20 SB, a polymericMDI.

The synergist component useful in the resin binders of the presentinvention includes lower N-alkylpyrrolidones. In general, the C1-C4N-alkylpyrrolidones are useful in the present invention, with thepreferred N-alkylpyrrolidone being N-Methyl-2-pyrrolidone. Other usefulsynergists include gamma-butyrolactone. Mixtures of the above synergistscan also be used to form the synergist component.

The resin binder of the present invention can also contain othersolvents, so long as the physical properties of the resultinglignocellulosic article are not adversely affected. For example, it ispreferred to avoid xylene as a component of the resin binder, becausethe use of xylene leads to a lower value of internal bond in theresulting lignocellulosic article.

The resin binder can also contain other conventional additives, such asparting agents or wood preservatives. Suitable parting agents aredescribed fully below. When the resin binder includes such optionaladditives, efficiency is gained because the resin binder and any othernecessary ingredients can be coated onto the lignocellulosic particlesin a single step.

The synergist component can be combined with the polyisocyanatecomponent in an amount from 0.5 to 25 weight percent based on the totalweight of the binder resin. More preferably, the binder resin includesfrom 0.5 to 15 weight percent, and most preferably 0.5 to 10 weightpercent synergist based on the total weight of the binder resin. Thebinder resin preferably comprises from about 75 to 99.5 weight percentpolyisocyanate component, and more preferably from about 85 to 99 weightpercent polyisocyanate component based on the total weight.

The lignocellulosic particles can be derived from a variety of sources.They can come from wood and from other products such as bagasse, straw,flax residue, nut shells, cereal grain hulls, and mixtures thereof.Non-lignocellulosic materials in flake, fibrous or other particulateform, such as glass fiber, mica, asbestos, rubber, plastics and thelike, can be mixed with the lignocellulosic material. Thelignocellulosic particles can come from the process of comminuting smalllogs, industrial wood residue, branches, or rough pulpwood intoparticles in the form of sawdust, chips, flakes, wafer, strands, mediumdensity fibers (MDF), and the like. They can be prepared from variousspecies of hardwoods and softwoods. It is important that thelignocellulosic particles have a moisture content of from 2 to 15 weightpercent. In a further preferred embodiment the water content is from 3to 12 weight percent, and most preferably from 4 to 10 weight percent.The water is utilized during the curing of the binder resin. If thewater content is outside of this range the binder resin is not asefficient at forming the molded article.

The lignocellulosic particles can be produced by various conventionaltechniques. For example, pulpwood grade logs can be converted intoflakes in one operation with a conventional roundwood flaker.Alternatively, logs and logging residue can be cut into fingerlings onthe order of about 0.5 to 3.5 inches long with a conventional apparatus,and the fingerlings flaked in a conventional ring type flaker. The logsare preferably debarked before flaking.

The dimensions of the particles are not particularly critical. Flakescommonly have an average length of about 2 to 6 inches, and averagewidth of about 0.25 to 3 inches, and an average thickness of about 0.005to about 0.05 inches. Strands which are about 4 cm wide and 12 cm longcan be used to make laminated strand lumber, while strands about 0.3 cmwide and 25 cm long can be used to make parallel strand lumber.

The wood particles can be further milled prior to use in the process ofthe invention, if such is desired to produce a size more suitable forproducing the desired article. For example, hammer, wing beater, andtoothed disk mills may be used.

The lignocellulosic particles are resinated using the binder resindescribed above. The binder resin and the lignocellulosic particles aremixed or milled together during the formation of a resinatedlignocellulosic mixture. Generally, the binder resin can be sprayed ontothe particles while they are being agitated in suitable equipment. Tomaximize coverage of the particles, the binder resin is preferablyapplied by spraying droplets of the binder resin onto the particles asthey are being tumbled in a rotary blender or similar apparatus. Forexample, the particles can be resinated in a rotary drum blenderequipped with at least one spinning disk atomizer. One advantage of thepresent invention is that the binder resin forms smaller droplets thantypical polyisocyanate binder resins leading to better coverage of theparticles.

For testing on a lab scale, a simpler apparatus can suffice to resinatethe particles. For example, a 5 gallon can is provided with bafflesaround the interior sides, and a lid with a hole large enough to receivethe nozzle of a spray gun or other liquid delivery system, such as apump sprayer. It is preferred that the binder resin be delivered as aspray. The particles to be resinated are placed in a small rotaryblender. The blender is rotated to tumble the particles inside againstthe baffles, while the desired amount of binder resin is delivered witha spray device. After the desired amount of binder resin is delivered,the particles can be tumbled for a further time to effect the desiredmixing of the particles with the binder resin.

The amount of binder resin to be mixed with the lignocellulosicparticles in the resinating step is dependant upon several variablesincluding, the binder resin used, the size, moisture content and type ofparticles used, the intended use of the product, and the desiredproperties of the product. Generally, the amount of binder resin tomixed with the particles is from 1 to 10 weight percent based on thetotal weight of the resinated lignocellulosic mixture. In a preferredembodiment the amount of binder resin is from 1 to 4 weight percentbased on the total weight of the resinated lignocellulosic mixture.

The mixture produced during the resinating step is referred to in theart as a furnish. The resulting furnish, i.e., the mixture of flakes,binder resin, parting agent, and optionally, wax, wood preservativesand/or other additives, is formed into a single or multi-layered matthat is compressed into a particle board or flakeboard panel or anothercomposite article of the desired shape and dimensions. The mat can beformed in any suitable manner. For example, the furnish can be depositedon a plate-like carriage carried on an endless belt or conveyor from oneor more hoppers spaced above the belt. When a multi-layer mat is formed,a plurality of hoppers are used with each having a dispensing or forminghead extending across the width of the carriage for successivelydepositing a separate layer of the furnish as the carriage is movedbetween the forming heads. The mat thickness will vary depending uponsuch factors as the size and shape of the wood flakes, the particulartechnique used in forming the mat, the desired thickness and density ofthe final product and the pressure used during the press cycle. The matthickness usually is about 5 to 20 times the final thickness of thearticle. For example, for flakeboard or particle board panels of ½ inchthickness and a final density of about 35 lbs/ft³, the mat usually willbe about 3 to 6 inches thick. After mat formation, a paper overlay, likethat used in furniture panels or for exterior siding, can be applied tothe mat prior to pressing.

Press temperatures, pressures and times vary widely depending upon theshape, thickness and the desired density of the composite article, thesize and type of wood flakes, the moisture content of the wood flakes,and the specific binder used. The press temperature can be from about100° to 300° C. In order to minimize generation of internal steam andthe reduction of the moisture content of the final product below adesired level, e.g., about 8 to about 12%, the press temperaturepreferably is less than about 250° C. and most preferably from about180° to about 240° C. The pressure utilized is generally from about 300to about 800 pounds per square inch. Preferably the press time is from120 to 350 seconds. The press time utilized should be of sufficientduration to at least substantially cure the binder resin and to providea composite article of the desired shape, dimension and strength. Forthe manufacture of flakeboard or particle board panels, the press timedepends primarily upon the panel thickness of the article produced. Thepressure applied by the press is correlated with the press temperatureso that the moisture content of the final product is from about 8 to12%. For example, the press time is generally from about 200 to about300 seconds for a pressed article with a ½ inch thickness.

Oriented Strand Board Manufacture

Oriented strand board (OSB) can be made by the process of the inventionfrom a plurality of discrete generally oriented strands or strips ofwood hot pressed together using a binder resin, such as the binder resinof the present invention described above. The pieces or strips of woodare, for example, plywood or veneer strips having a width of about ¼inch to ⅜ inch, a length of about 2½ inches to about 3 inches and athickness of about 20 mils. The strips of wood are generally oriented sothat the fiber direction is approximately the same. The resinated,oriented strips are disposed into a press or mold so that the strips arein contact with other strips both vertically and horizontally so thatwhen pressed under heat and pressure the strips are compressed tightlyagainst other contacting strips to adhere the strips together and tomold a sheet of material having desired dimensions. The strands orstrips of wood material are not perfectly aligned in one fiber direction(approximately ±20 ° from a single direction) so that some stripsoverlap other adjacent strips for stronger adhesion.

Oriented strand boards are prepared in a pilot plant according to theprocess described above. The strands are obtained from a commercial milland are predominantly poplar. The strands are resinated in a rotary drumblender equipped with at least one single spinning disk atomizer using2.5 weight percent of the binder resin. Such blenders are known in theart and are available from suppliers such as Coil Manufacturing, theytypically include up to six spinning disk atomizers in each blender. Thepress cycle is a total of 4 minutes with a press temperature of about205° C. A commercially available external release agent, a water basedorganosiloxane emulsion, is coated on the inner mold surfaces. Thetarget size of the boards is 2 feet by 2 feet by {fraction (7/16)} inch,with a density of 39 pounds per cubic foot. A total of 24 boards areproduced. Twelve of the boards are produced by a conventional process,wherein the resination step is accomplished with a binder resincontaining only Lupranate® M20 SB (“M20SB”), a polymeric MDI materialsold by BASF Corporation. The other twelve are produced by the processof the current invention, wherein the binder resin contains 10 weightpercent of N-methyl-2-pyrrolidone (“NMP”) and 90 weight percent ofLupranate® M20 SB. Eight boards, four from each group of twelve, wererandomly chosen for evaluation of average density and-internal bondstrength (IB). The results are given in Table 1.

In Table 1, the IB is given in units of pounds per square inch, or psi.Internal bond strength, is a commonly measured parameter oflignocellulosic articles manufactured by pressing binder coated woodparticles at high temperature and pressure. It measures theeffectiveness of the binder resin. The higher the IB, the stronger isthe article or board made by the process. For Table 1, IB is measuredaccording to ASTM D-1037.

TABLE 1 ORIENTED STRAND BOARDS Density, IB Example Binder Resincomposition (lbs/ft³⁾ (psi) 1 100% M20SB 38.7 51.8 2 100% M20SB 39 56.13 100% M20SB 38.1 39.0 4 100% M20SB 40.4 45.5 5  90% M20SB + 10% NMP40.4 63.9 6  90% M20SB + 10% NMP 39.9 55.3 7  90% M20SB + 10% NMP 40.252.1 8  90% M20SB + 10% NMP 39 51.6 Average 100% M20SB 38.8 48.1 Average 90% M20SB + 10% NMP 39.9 55.7

It is seen from Table 1 that boards made using a binder resin where 10%of the polymeric MDI is replaced by NMP are at least as strong, based onmeasurement of IB, as are boards made using a binder which is 100% MDI.In fact, the results suggest that the NMP enhances the strength of theformed internal bonds (average of 55.7 with 10% NMP versus 48.1 with noNMP). While not wishing to be bound by any particular theory it isbelieved that the NMP dissolves the lignin in the lignocellulosicmaterial thereby enhancing the penetration of the binder resin and itsadhesion to the lignocellulosic particles.

In another experiment boards are prepared as described above usingseveral levels of NMP and the viscosity of the binder resin is measuredin addition to IB. The results below in Table 2.

TABLE 2 ORIENTED STRAND BOARDS Viscosity at 25° Density, IB ExampleBinder resin composition (centipoise) (lbs/ft³⁾ (psi) 1 100% M20SB 20938.9 54 2  95% M20SB + 5% NMP 130 * * 3  90% M20SB + 10% NMP  83 39.956 * not determined

The results demonstrate the significant reduction of viscosity providedby the present binder resin without a reduction in the internal bondstrength that would be expected based on typical solvents.

The present invention further teaches a parting agent, which comprisesthe reaction production of an isocyanate compound and anisocyanate-reactive compound for use with the binder resin of thepresent invention.

The isocyanate compounds useful in the parting agent comprise theorganic di- and polyisocyanates, modified isocyanates,isocyanate-terminated prepolymers, and mixtures of these isocyanates,all described below.

The isocyanate compound which may be used includes aliphatic, alicyclicand aromatic polyisocyanates characterized by containing two or moreisocyanate groups. Such polyisocyanates include the diisocyanates andhigher functionality isocyanates, particularly the aromaticpolyisocyanates. Mixtures of polyisocyanates may also be used andinclude, crude mixtures of di- and higher functionality polyisocyanatesproduced by phosgenation of aniline-formaldehyde condensates or asprepared by the thermal decomposition of the corresponding carbamatesdissolved in a suitable solvent, as described in U.S. Pat. No. 3,962,302and U.S. Pat. No. 3,919,279, both known as crude diphenylmethanediisocyanate (MDI) or polymeric MDI.

The organic polyisocyanate may be an isocyanate-terminated prepolymerprepared by reacting, an excess of a polyisocyanate with a polyol which,on a polyisocyanate to polyol basis, may range from about 20:1 to 2:1.The polyols include, for example, polyethylene glycol, polypropyleneglycol, diethylene glycol monobutyl ether, ethylene glycol monoethylether, triethylene glycol, etc., as well as glycols or polyglycolspartially esterified with carboxylic acids including all polyesterpolyols, and all polyether polyalkylene polyols. Such polyols are wellknown in the art and will not be further described.

The isocyanate compound may also be modified isocyanates, such as,carbodiimides, allophanates, isocyanurates, and biurets.

Also illustrative of the di- or polyisocyanates which may be employedare, for example: toluene-2,4- and 2,6-diisocyanates or mixturesthereof; diphenylmethane-4,4′-diisocyanate anddiphenylmethane-2,4′-diisocyanate or mixtures of same, the mixturespreferably containing about 10 parts by weight 2,4′-MDI or higher,making them liquid at room temperature; polymethylene polyphenylisocyanates; naphthalene-1,5-diisocyanate; 3,3′-dimethyldiphenylmethane4,4′-diisocyanate; triphenyl-methane triisocyanate;hexamethylene diisocyanate; 3,3′-ditolylene-4,4-diisocyanate; butylene1,4-diisocyanate; octylene-1,8-diisocyanate; 4-chloro-1,3-phenylenediisocyanate; 1,4-, 1,3-, and 1,2-cyclohexylene diisocyanates and; ingeneral, the polyisocyanates disclosed in U.S. Pat. No. 3,577,358, thedisclosure of which is incorporated herein by reference. Preferredpolyisocyanates include 2,4′-MDI, 4,4′-MDI, 2,2′-MDI, polymeric MDI, andmixtures thereof.

Typical of the suitable polyisocyanates are those sold under thetrademark Lupranate® by BASF Corporation. For example, Lupranate® MI, anisomeric blend of 2,4′ and 4, 4′ MDI isomers, or Lupranate® M20 SB, apolymeric MDI.

The isocyanate-reactive compound can be represented by the generalstructure R(ao)_(n)Y. Here Y represents a monofunctional group which isreactive with isocyanates. Examples include monoalkylamino and hydroxyl,with hydroxyl being preferred. In the structure above, (ao) representsan alkylene oxide or mixture of alkylene oxides such as ethylene oxide,propylene oxide, butylene oxide, and mixtures thereof; n refers to thenumber of alkylene oxide units in the isocyanate-reactive compound. Itis conventional to use the symbol (ao)_(n) to represent apolyoxyalkylene chain comprising, on average, n repeating units ofalkylene oxide. In the invention, a preferred alkylene oxide is ethyleneoxide. The variable n can be integer or non-integer and is in generalfrom about 1 to about 25, more preferably from about 2 to about 25, andmost preferably from about 3 to about 10.

In the isocyanate reactive compound R—(ao)_(n)—Y, R represents ahydrophobic group. The hydrophobic group is based either on hydrocarbonsor on silicon-containing compounds.

Preferred hydrocarbon hydrophobic groups include in general thosecontaining alkyl, alkaryl or polyaryl moieties. Alkyl moieties useful inthe invention include those with about 6 or more carbon atoms. Examplesare hexyl, octyl, nonyl, decyl, dodecyl, and hexadecyl. Useful alkarylmoieties include the aryl hydrocarbons such as alkaryl, dialkaryl, andtrialkaryl hydrocarbons, wherein the alkyl groups contain at least about3 carbon atoms. Together with the 6 carbon atoms of the aromatic ring,there are thus 9 or more carbon atoms in the preferred alkaryl,dialkaryl, and trialkaryl hydrocarbons. Examples include octylphenyl,hexylphenyl, nonylphenyl, dioctylphenyl, dinonylphenyl, trioctylphenyl,trinonylphenyl, and trialkarylphenyl groups. Particularly preferred arethe alkaryl and dialkaryl groups such as nonylphenyl and dinonylphenyl.The polyaryl compounds have the general structure of a polyphenylstructure that is either alkyl substituted or unsubstituted. Thus in thepresent specification and claims the term polyaryl means a polyphenylstructure that is either alkyl substituted or unsubstituted.

Examples of isocyanate-reactive compounds useful in the invention thusinclude alcohol alkoxylates, alkylphenol alkoxylates, and dialkylphenolalkoxylates. Examples of alcohol alkoxylates include the fatty alcoholethoxylates which are made by adding 2-20 units of ethylene oxide onto aC₆-C₁₈ straight chain or branched alcohol. These are availablecommercially, for example, under the Iconol® trademark from BASFCorporation. Examples of useful alkylphenol alkoxylates include thosemade from alkylphenols having three or more carbons in the alkyl chainattached to the phenol ring. Commonly available commercial alkylphenolalkoxylates include octylphenol ethoxylates and nonylphenol ethoxylateswhich are made by adding about 2 to about 20 units of ethylene oxide tooctylphenol or nonylphenol. They are sold, for example, under thetradenames Iconol® OP and Iconol® NP by BASF Corporation. Similarly,dialkylphenol ethoxylates are useful in the invention. Examples arealkoxylates of those dialkylphenols or trialkylphenols having three ormore carbon atoms in each alkyl group. Especially preferred are theethoxylates of dialkyl- or trialkylphenols made by adding about 2 toabout 20 units of ethylene oxide to, for example, a dialkylphenol suchas dioctylphenol or dinonylphenol. Dinonylphenol ethoxylates areavailable commercially from BASF Corporation under the Macol® DNPtradename.

Where R represents silicon-containing compounds, the preferredhydrophobic group comprises siloxane groups. Generally preferred are thedimethylsiloxanes including trisiloxanes and higher polysiloxanes. Apreferred isocyanate-reactive compound comprises a silicone compound ofgeneral structure

wherein Q is a bridging group of one or more atoms, m is 0-10, p is0-10, R1 and R2 are independently alkyl or alkaryl groups containing 1to 18 carbon atoms, (ao) is an alkylene oxide or mixture of alkyleneoxides selected from the group consisting of ethylene oxide, propyleneoxide, butylene oxide, and mixtures thereof, Y represents amonoftinctional isocyanate reactive group, and n is from about 2 toabout 20.

Preferably R1 and R2 are alkyl groups containing 1-10 carbon atoms. Morepreferably, R1 and R2 contain 1-4 carbon atoms. Most preferably, R1 andR2 are methyl. R1 and R2 may be different, but it is preferred that theybe the same. It is particularly preferred that R1 and R2 are bothmethyl. The subscripts m and p are preferably from zero to 2; in aparticularly preferred embodiment, m and p are both zero. When m and pare both zero, the compound is a trisiloxane. Where the sum of m and pis greater than zero, the compound is a higher polysiloxane. Aparticularly preferred trisiloxane containing isocyanate-reactivecompound is commercially available from BASF Corporation as Masil®SF-19.

Such silicon containing isocyanate-reactive compounds can besynthesized, for example, by the reaction of R1,R2-terminatedhydro-functional polysiloxane of general structure

where R1, R2, m, and p have the same meaning as above, with an adduct ofan unsaturated alcohol and alkylene oxides. The adduct can be preparedby reacting the unsaturated alcohol with ethylene oxide or a mixture ofalkylene oxides in the presence of base catalysis. Thus, when theunsaturated alcohol is allyl alcohol, the adduct will have the generalstructure CH₂═CH—CH₂—(ao)_(n)—OH, where ao represents the ethylene oxideunits or mixture of alkylene oxide units, and n represents the degree ofalkoxylation. When the olefin of the allyl alcohol adduct reacts withthe Si-H bond of the hydro-functional polysiloxane, a bridging group Qis formed consisting of the three carbon atoms of the ally alcoholportion of the adduct.

When Y of the isocyanate reactive compound comprises a hydroxyl groupthe reaction product will contain urethane linkages formed from thereaction of the isocyanate groups of the isocyanate compound with thehydroxyl group of the isocyanate-reactive compound. Similarly when Ycomprises an alkylamino or other nitrogen containing isocyanate-reactivegroup, the resulting reaction product will contain urea linkages, basedon the reaction of the isocyanate groups with the nitrogen of theisocyanate-reactive compound.

The parting agents of the present invention may also contain chemicalmodifications of the urethane or urea linkage, such as allophanates,carbodiimides, biurets, and uretonimines. In general allophanatelinkages are formed from the reaction of an isocyanate group with aurethane group. Generally the allophanate reaction is carried out withspecial allophanate catalysts and at a temperature relatively higherthan that at which the urethane is formed from the reaction ofisocyanate and hydroxyl.

The parting agent of the present invention can be prepared orsynthesized by a number of routes. In general, an isocyanate compoundand an isocyanate-reactive compound of general structure R(ao)_(n) Y arecharged together into a reaction vessel.

Thereafter, they are allowed to react for a time sufficient to react outsubstantially all of the Y groups on the isocyanate-reactive compoundand all of the isocyanate groups on the isocyanate compound Preferablythere is less than 2.5 % residual free NCO after the formation of theparting agent, more preferably less than 1.0% and most preferably lessthan or equal to 0.2% free NCO after the reaction is complete. It isdesirable to have these very low levels of free NCO when using theparting agent in a binder resin for wood particles, as described below.These low levels of free NCO prevent migration of the parting agent intothe wood particles. Excess isocyanate reactive compound can be toleratedbecause it does not present any such problem.

Where the isocyanate compound and isocyanate-reactive compound arecharged in stoichiometrically equivalent amounts, there is produced aparting agent which contains either urethane linkages or urea linkages,depending on whether Y in the isocyanate-reactive compound is a hydroxylgroup or an alkylamino group, respectively. For this reaction thereaction temperature is set at a temperature of about 40° C. to about100° C. Higher or lower temperatures can also be used, but the givenrange provides good results. The reaction can be monitored by followingthe isocyanate number of the reaction product over time. The reactioncan be stopped when the desired isocyanate number is reached. Thereaction will proceed without catalysts. However urethane catalysts maybe added to the reaction mixture. Examples of suitable catalysts includepotassium octoate, zinc acetylacetonate, potassium hydroxide, and organotin compounds.

To form parting agents which contain allophanate linkages, further stepsare required. For example, after charging the isocyanate compound andthe isocyanate-reactive compound in stoichiometrically equivalentamounts and reacting at a temperature of from about 40° C. to about 100°C. until the desired intermediate isocyanate number is reached, a secondcharge of the isocyanate compound can be added to the reaction vessel.Further reaction is then carried out at a second temperature higher thanabout 40° C. to about 100° C. for a period of time sufficient to reactsubstantially all of the isocyanate added in the second charge. Alongwith the second charge of isocyanate compound, it is generally necessaryto also add a catalyst which aids in the formation of the allophanategroups. Such allophanate catalysts are known in the art and include zincacetylacetonate, titanium tetrabutoxide, and ferric chloride. Theallophanate reaction is preferably carried out at a temperature of about100° C. to about 150° C.

An alternative method for producing parting agents containingallophanate groups is as follows. First an isocyanate compound and anisocyanate-reactive compound are charged to a reaction vessel in anamount such that the molar ratio of the isocyanate compound toR(ao)_(n)Y is greater then 1:1, that is, such that there is a molarequivalent excess of the isocyanate compound in the reaction vessel. Themixture thus charged is then reacted at a temperature of from about 40°C. to about 100° C. until substantially all of the R(ao)_(n)Y hasreacted. The reaction can be monitored by following the free isocyanatenumber during the reaction. When the desired intermediate % free NCO isreached, the mixture is then reacted at a second temperature higher thanabout 40° C. to about 100° C. The reaction proceeds until substantiallyall of the isocyanate compound has reacted and the isocyanate content ofthe reaction product is equal to or less than the desired level.

Although if the reaction is carried out at high temperatures for asufficiently long time, an allophanate catalyst is not absolutelyrequired, it is in general preferred in the last step to also addconventional allophanate forming catalysts such as those describedabove. The allophanate catalysts may be charged to the vessel prior tothe reaction at the first temperature of from about 40° C. to about 100°C. Alternatively, the allophanate catalysts may be charged afterreacting at the first temperature but prior to the reaction at thesecond higher temperature. In general, the allophanate catalyst and thetemperature of reaction are chosen such that during the reaction of theisocyanate compound and isocyanate-reactive compound in the first step,the temperature is lower than that required for efficient allophanateformation. In the reaction at the second temperature the temperature ishigh enough to efficiently convert the remaining isocyanate groups toallophanate.

Allophanates can be formed when an amount of isocyanate compound instoichiometric excess to that of the isocyanate-reactive compound ischarged to the reaction vessel. As discussed above, the charge of excessisocyanate compound can be accomplished in the first step along with thecharge of isocyanate-reactive compound, where the conditions ofcatalysis and temperature are such that the excess isocyanate will notreact further with the urethane or urea linkage being formed in thereaction of the isocyanate compound and the isocyanate-reactivecompound. Alternatively, the excess isocyanate can be introducedfollowing the reaction of stoichiometric amounts of isocyanate-reactivecompound and isocyanate compound.

In either case, in general, any amount of excess isocyanate can be addedto the reaction mixture. However, it is preferred in making the partingagent of the present invention to use an excess of isocyanate compoundon the order of about 1 to 10 equivalent percent. That is, there shouldpreferably be about a 1 to 10 percent excess of isocyanate groups overisocyanate-reactive groups. It can thus be seen that when parting agentsof the present invention are made which contain allophanate linkages,the compositions will also in general contain urea or urethane linkages.

The parting agent and the organic di- or polyisocyanate which comprisesthe binder resin should be chosen such that they are compatible. Thatis, the two components should be readily soluble in each other, so thata single phase composition can be obtained. To this end, it is preferredthat the organic di- or polyisocyanate and the isocyanate compound onwhich the parting agent is based should have a similar structure.Therefore, a preferred binder resin is one where the organic di- orpolyisocyanate comprises an aromatic di- or polyisocyanate and whereinthe isocyanate compound on which the parting agent is based is alsoaromatic.

Preferred organic di- or polyisocyanate include methylenediphenyldiisocyanate isomers such as 2,4′-MDI, 4,4′-MDI, 2,2′-MDI. A suitableisocyanate compound is Lupranate® MI, which is a mixture of 2,4′ and4,4′-MDI isomers, available from BASF Corporation. Another preferredorganic di- or polyisocyanate is polymeric MDI. Mixtures of the abovepreferred di- or polyisocyanates may also be used. A particularlypreferred polyisocyanate comprises polymeric MDI. A useful commerciallyavailable polymeric MDI material is Lupranate® M20S isocyanate sold byBASF Corporation.

PARTING AGENT EXAMPLES

Example 1 below describes the synthesis of a parting agent wherein theisocyanate compound is a mixture of diphenylmethane diisocyanateisomers, R comprises dialkaryl, Y is hydroxyl, and n is about 10.Example 2 describes the synthesis of a parting agent wherein theisocyanate compound is a mixture of diphenylmethane diisocyanateisomers, R comprises trisiloxane, and Y is hydroxyl. Example 3demonstrates formation of a parting agent wherein the hydrophobic groupis an alkaryl. Example 4 is similar to Example 3 with the addition of acatalyst.

Lupranate® MI isocyanate is a mixture of diphenylmethylene diisocyanatessold by BASF Corporation. Macol® DNP-IO is an average 10 mole ethoxylateof dinonylphenol, and Iconol® NP-6 is an average 6 mole ethoxylate ofnonylphenol; they are commercially available from BASF Corporation.

Example 1 Synthesis of an Internal Parting Agent Where the HydrophobicGroup is Dialkaryl

Macol® DNP-10 surfactant (428.4 g) is placed in a one liter two neckflask and heated to 45° C. With continuous agitation, Lupranate® MIisocyanate (71.6 g) is added dropwise over a period of an hour. Thetemperature is increased to 80° C. and the reaction is continued for 20to 24 hours. Titration of remaining free NCO groups shows a % free NCOof about 0.5%. The temperature is maintained for an additional one hour,the reaction mixture is cooled to room temperature and allowed to standovernight. Titration of free NCO after the overnight period shows thereaction is complete—that is, the measured free NCO is 0.1%, which iswithin the error of the method.

Example 2 Synthesis of an Internal Parting Agent Where the HydrophobicGroup is Silicon

Masil® SF-19 surfactant (423 g) is placed in a one liter three neckflask and heated to 80° C. with continuous agitation provided by anoverhead stirrer. Lupranate® MI isocyanate (77g) is added dropwise overa period of about 30 minutes. The temperature is increased to 90° C. andthe reaction is continued for 20-24 hours, after which time the % freeNCO is determined by titration and found to be ca. 0.5%. The reaction iscontinued for an additional 2 hours at 90° C., the reaction mixturecooled to room temperature and allowed to stand overnight. Titration offree NCO shows the reaction is complete.

Example 3 Synthesis of an Internal Parting Agent Where the HydrophobicGroup is Alkaryl.

Iconol® NP-6 (393.5 g) is placed in a one liter two neck flask andheated to 45° C. With continuous agitation, Lupranate® MI (106.5 g) isadded dropwise over a period of an hour. The temperature is increased to80° C. and the reaction is continued for 20 to 24 hours. Titration ofremaining free NCO groups shows a % free NCO of about 0.5%. Thetemperature is maintained for an additional one hour, the reactionmixture is cooled to room temperature and allowed to stand overnight.Titration of NCO the following morning shows the free NCO is 0.1%, whichis within the error of the method, thus the reaction is complete.

Example 4 Synthesis of an Internal Parting Agent Where the HydrophobicGroup is Alkaryl.

Lupranate® MI (106.5 g) is placed in a one liter two neck flask andheated to 45° C. With continuous agitation, Iconol® NP-6 (393.5 g) and20 ppm of the urethane catalyst DABCO T-12 is added dropwise over aperiod of an hour. The temperature is increased to 80° C. and thereaction is continued for 9 hours. Titration of remaining free NCOgroups shows a % free NCO of about 0.5%. The temperature is maintainedfor an additional one hour, the reaction mixture is cooled to roomtemperature and allowed to stand overnight. Titration of NCO thefollowing morning shows the free NCO is 0.1%, which is within the errorof the method, thus the reaction is complete.

Procedure For Evaluation Of Parting Agent

The following procedure was used to test the parting agents of thepresent invention prepared as in Examples 1—3. Results of theexperiments are given in Table 3 below.

1. The stainless steel caul plates are preconditioned with external moldrelease (i.e. spray a dilute solution of external press release on thecaul plate, then wipe off the excess with a paper towel). In theExamples, XCTW-9495, a water based organosiloxane was used as theexternal mold release.

2. Raw material (wood fiber, wood flake, wood particle, saw dust, etc.)is blended with a binder resin comprising Lupranate® M20SB, a polymericMDI sold by BASF Corporation, a parting agent prepared in accordancewith the present invention, and, optionally, a synergist component toform a furnish material. The optional synergists include the lowerN-alkyl pyrrolidones. In general, the C₁-C₄ N-alkylpyrrolidones areuseful in the present invention, with the preferred N-alkyl pyrrolidonebeing N-methyl-2-pyrrolidone (NMP). Other useful synergists includegamma-butyrolactone. Mixtures of the above synergists can also be usedto form the synergist component. The synergist component can be combinedwith the polyisocyanate component in an amount of from 0.5 to 25 weightpercent based on the total weight of the binder resin. More preferably,the binder resin includes from about 0.5 to 15 weight percent, and mostpreferably from about 0.5 to 10 weight percent synergist based on thetotal weight of the binder resin.

3. The parting agent and synergist used, are reported in the Examples asweight percent based on the total weight of the binder resin. Between2.5% and 10% by weight binder resin is used, based on the total weightof the raw material lignocellulosic particles. The amount used isreported in the Examples. In the Examples, the lignocellulosic particlesare either sawdust or medium density fibers (MDF).

4. A form is used to set the desired size of the board, the furnishmaterial is layered on the bottom caul plate. In the Examples, a 6 inchby 11 inch aluminum form is used. The caul plate is transferred into thepress and covered with another preconditioned caul plate.

5. The material is pressed under heat and pressure to produce a boardusing typical conditions. Pressing time and temperature vary with boardthickness and the raw material. In the Examples, the boards are pressedfor 2 minutes at 350° F. and 520 psi. The press is opened and the caulplates and board are removed from the press.

6. A successful event is one after which the board (a) is readilyremoved from caul plates without difficulty, (b) without leaving residueon the caul plates and (c) without causing surface imperfections on theboard resulting from sticking.

7. Repeat steps 2-5 using the same set of caul plates without applyingany additional external press release.

8. The number of boards successfully made is a measure of theperformance of the parting agent. The higher the number, the better theparting agent. The percent binder resin used is a weight percent basedon the total weight of the raw material.

TABLE 3 Wt. % Parting parting Wt. % # agent agent in Wt. % synergist inof Exam- Raw in binder binder binder the binder boards ple materialresin resin used resin pressed 1 MDF Example 3 10  4 none 5 2 MDFExample 2 10  4 none 9 3 MDF Example 2 10  4 10% NMP  6 4 MDF Example 25 4 5% NMP 6 5 Sawdust Example 1 5 4 none 7 6 MDF Example 1 5 4 5% NMP12  7 MDF None 0 4 none 1

Example 7 is a control where no parting agent was used in the binderresin. With no parting agent, only one board could be pressed beforere-applying the external release agent. Examples 1-6 show that theparting agents of the present invention impart desirable properties tothe binder resins of the present invention, in that their use in thebinder resins enables 5 to 12 boards to be pressed withoutre-application of the external release agent.

In addition, all binder resins in Examples 1-6 are of a single phase andhomogeneous, indicating that the parting agent is compatible with thedi- or polyisocyanate, and that the binder resins are stable.

The foregoing invention has been described in accordance with therelevant legal standards, thus the description is exemplary rather thanlimiting in nature. Variations and modifications to the disclosedembodiment may become apparent to those skilled in the art and do comewithin the scope of the invention. Accordingly, the scope of legalprotection afforded this invention can only be determined by studyingthe following claims.

We claim:
 1. A method for preparing a compression molded or pressedlignocellulosic article comprising the steps of: a) forming a binderresin by combining from about 75 to 99.5 weight percent based on thetotal weight of the binder resin of a polyisocyanate component with fromabout 25 to 0.5 weight percent based on the total weight of the binderresin of a parting agent, the parting agent comprising the reactionproduct of an isocyanate compound and an isocyanate-reactive compound ofthe general structure R—(ao)_(n)—Y  wherein R is a hydrophobic groupcontaining alkyl, alkaryl, or polyaryl, moieties, wherein the alkylmoieties comprise straight chain or branched hydrocarbons with 6 or morecarbon atoms, the alkaryl moieties comprise monoalkyl, dialkyl, ortrialkyl substituted aromatic hydrocarbons with 9 or more carbon atoms,and the polyaryl moieties comprise a polyphenyl structure that is eitheralkyl substituted or unsubstituted; (ao) is an alkylene oxide or mixtureof alkylene oxides selected from the group consisting of ethylene oxide,propylene oxide, butylene oxide, and mixtures thereof; n is from 1 to25; and Y represents a monofunctional isocyanate-reactive group; b)forming a resinated lignocellulosic mixture by combining from about 1 to10 weight percent based on the total weight of the lignocellulosicmixture of the binder resin with from about 99 to 90 weight percentbased on the total weight of the lignocellulosic mixture oflignocellulosic particles, the lignocellulosic particles having amoisture content of from 2 to 15 weight percent; and c) forming acompression molded or pressed lignocellulosic article by compressing theresinated lignocellulosic mixture at an elevated temperature and underpressure.
 2. The method according to claim 1, comprising forming theparting agent with an aromatic isocyanate compound.
 3. The methodaccording to claim 1, comprising forming the parting agent with anisocyanate-reactive compound wherein R comprises a polyaryl group. 4.The method according to claim 3, comprising forming the parting agentwith an isocyanate-reactive compound wherein n is from 1 to
 10. 5. Themethod according to claim 1, comprising forming the binder resin and theparting agent with one or more isocyanates selected from the groupconsisting of diphenylmethane-2,4′-dilsocyanate,diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,2′-diisocyanate,polymeric diphenylmethyl diisocyanate, and mixtures thereof.
 6. Themethod according to claim 1, wherein step a) comprises combining fromabout 90 to about 99.5 percent by weight of said polyisocyanatecomponent with from about 0.5 to about 10 percent by weight of saidparting agent.
 7. The method according to claim 1, wherein step a)further comprises adding from 0.5 to 15 weight percent based on thetotal weight of a synergist selected from the group consisting of C₁₋₄N-alkylpyrrolidones, gamma-butyrolactone, and mixtures thereof to thebinder resin.
 8. The method according to claim 7, comprising addingN-methyl-2-pyrrolidone as the synergist.
 9. The method according toclaim 1, wherein the temperature is elevated to from 100 to 300° C. 10.The method according to claim 9, wherein the temperature is elevated tofrom 180 to 240° C.
 11. The method according to claim 1, comprisingsetting the pressure at from 300 to 800 pounds per square inch.
 12. Themethod according to claim 1, wherein step c) further comprisescompressing the resinated lignocellulosic mixture for from 200 to 300seconds.
 13. A method according to claim 1 wherein step c) comprisesforming a compression molded or pressed lignocellulosic board.
 14. Themethod according to claim 1, wherein step b) comprises forming theresinated lignocellulosic mixture by combining the binder resin withlignocellulosic particles having a moisture content of from 3 to 12weight percent.
 15. The method according to claim 1, wherein step b)comprises forming the resinated lignocellulosic mixture by combining thebinder resin with lignocellulosic particles having a moisture content offrom 4 to 10 weight percent.
 16. The method according to claim 1,wherein step a) comprises forming the parting agent using anisocyanate-reactive compound where Y is either a hydroxyl group or amonoalkyl group.
 17. The method according to claim 1, wherein theparting agent is formed by combining at least one MDI isomer with anisocyanate-reactive compound where R comprises an alkaryl and Y is ahydroxyl group.
 18. The method according to claim 17, wherein theparting agent is formed with an isocyanate-reactive compound where n isfrom 1 to
 10. 19. The method according to claim 1, wherein the partingagent is formed by combining at least one MDI isomer with an isocyanatereactive compound where R comprises a polyalkaryl and Y is a hydroxylgroup.
 20. The method according to claim 19, wherein the parting agentis formed from an isocyanate-reactive compound where n is from 1 to 10.